A 13C field-cycling NMR relaxometry investigation of proton tunnelling in the hydrogen bond: Dynamic isotope effects, the influence of heteronuclear interactions and coupled relaxation

Abstract

Concerted double proton transfer in the hydrogen bonds of a carboxylic acid dimer has been studied using 13C field-cycling NMR relaxometry. Heteronuclear 13C– 1H dipolar interactions dominate the 13C spin–lattice relaxation which is significantly influenced by the polarisation state of the 1H Zeeman reservoir. The methodology of field-cycling experiments for such heteronuclear spin-coupled systems is studied experimentally and theoretically, including an investigation of various saturation-recovery and polarisation-recovery pulse sequence schemes. A theoretical model of the spin–lattice relaxation of this coupled system is presented which is corroborated by experiment. Spectral density components with frequencies ω C, ω C + ω H, and ω C − ω H are mapped out experimentally from the magnetic field dependence of the 13C and 1H spin–lattice relaxation and the proton transfer rate at low temperature is determined from their widths. Any dynamic isotope effect on the proton tunnelling in the hydrogen bond arising from 13C enrichment in the skeletal framework of the dimer is found to be smaller than experimental uncertainties (approximately 5%).